Method of manufacturing of polymer-coated particles for chemical mechanical polishing

ABSTRACT

A method of manufacturing polymer-coated particles is useful for chemical mechanical polishing magnetic, optical, semiconductor or silicon substrates. First it provides a dispersion of particle cores in a non-aqueous solvent. Then introducing a polymeric precursor into the dispersion to react the polymeric precursor forms a polymer. The polymer coats at least a portion of the surface of the particle cores with the polymer and forms the polymer-coated particles having a solid outer polymeric shell. Substituting the non-aqueous solvent with water forms an aqueous mixture containing the polymer-coated particles. And it forms an aqueous chemical mechanical polishing formulation with the polymer-coated particles without drying the polymer-coated particles.

BACKGROUND

This disclosure relates to the polishing of magnetic, optical,semiconductor and silicon wafers and more particularly, to polishingcompositions and methods for polishing and planarizing silicon wafers.

The semiconductor industry uses interconnect metals in formingintegrated circuits on semiconductor wafers. These interconnect metalsare preferably non-ferrous metals. Suitable examples of such non-ferrousinterconnects are aluminum, copper, gold, nickel, and platinum groupmetals, silver, tungsten and alloys comprising at least one of theforegoing metals. These interconnect metals have a low electricalresistivity. Copper metal interconnects provide excellent conductivityat a low cost. Because copper diffuses into many dielectric materials,such as silicon dioxide or doped versions of silicon dioxide, integratedcircuit fabricators typically apply a diffusion barrier layer to preventthe copper diffusion into the dielectric layer. For example, barrierlayers for protecting dielectrics include, tantalum, tantalum nitride,silicon nitride, tantalum-silicon nitrides, titanium, titanium nitrides,titanium-silicon nitrides, titanium-titanium nitrides,titanium-tungsten, tungsten, tungsten nitrides and tungsten-siliconnitrides.

In the manufacturing of semiconductor wafers, polishing compositions areused to polish semiconductor substrates after the deposition of themetal interconnect layers. Typically, the polishing process uses a“first-step” slurry specifically designed to rapidly remove theexcessive interconnect metal. The polishing process then includes a“second-step” slurry to remove the barrier layer. The second-step slurryselectively removes the barrier layer without adversely impacting thephysical structure or electrical properties of the interconnectstructure. In addition to this, the second step slurry should alsodisplay low erosion for dielectrics.

While the “two-step” slurry generally performs satisfactorily in presentconditions, it is desirable to have polishing compositions that can beused for planarizing the metal interconnect without substantial dishingof the interconnect metal and scratching of the wafer surface.

Preparation and evaluation of chemically modified abrasives for chemicalmechanical polishing by Partch et al. in an abstract presented atMaterials Research Society (MRS) meeting in 2001, discloses coatingindividual particle cores with a layer of organic or inorganic material.However, Partch et al., disclosed manufacturing the polishingcomposition with abrasive particles having a large particle sizedistribution that resulted in scratching and other forms of surfacedamage.

U.S. Pat. Pub. No. 2004/0060502 to Singh discloses a plurality ofparticles that may be coated by weakly or strongly adsorbing surfactantsor polymer additives to a core particle. The polymers thus adsorbed ontothe abrasive particles can desorb from the particles during thepolishing process to alter polishing characteristics and possibly resultin damage to the polished surface.

There thus remains an unsatisfied demand for a method of manufacturingpolymer-coated particles suitable for chemical mechanical polishing ofmagnetic, optical, semiconductor or silicon substrates.

SUMMARY OF THE INVENTION

The invention provides a method of manufacturing polymer-coatedparticles useful for chemical mechanical polishing magnetic, optical,semiconductor or silicon substrates comprising: providing a dispersionof particle cores in a non-aqueous solvent; introducing a polymericprecursor into the dispersion to react the polymeric precursor to form apolymer, the polymer coating at least a portion of the surface of theparticle cores with the polymer and forming the polymer-coated particleshaving a solid outer polymeric shell; substituting the non-aqueoussolvent with water to form an aqueous mixture containing thepolymer-coated particles; and forming an aqueous chemical mechanicalpolishing formulation with the polymer-coated particles without dryingthe polymer-coated particles.

In another aspect, a method of manufacturing polymer-coated particlesuseful for chemical mechanical polishing magnetic, optical,semiconductor or silicon substrates comprising: providing a dispersionof particle cores in a non-aqueous solvent; introducing a polymericprecursor into the dispersion to react the polymeric precursor to form apolymer, the polymer coating at least a portion of the surface of theparticle cores with the polymer and forming the polymer-coated particleshaving a solid outer polymeric shell; substituting the non-aqueoussolvent with water to form an aqueous mixture containing thepolymer-coated particles; and forming an aqueous chemical mechanicalpolishing formulation with an aqueous dispersion of the polymer-coatedparticles without drying the polymer-coated particles.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The method produces polymer-coated particles useful for chemicalmechanical polishing by first dispersing core particles in a non-aqueoussolvent. Preferably, mixing or agitating the solvent maintains theparticles in suspension. The non-aqueous solvent facilitates reacting apolymeric precursor to form a polymer. This polymer coats at least aportion of the surface of the core particles with the polymer to formthe polymer-coated particles. Preferably the polymer-coated particle hasa physisorbed structure surrounding the particle core. For purposes ofthis specification, physisorbed structure represents a coating lacking achemical bond to the particle. The core particles have a hardnessgreater than the solid outer polymeric shell. Controlling the thicknessof the polymeric shells allows the polymer-coated particles to achievehybrid polishing properties different than polymer particles anddifferent than conventional abrasive particles, such as alumina, ceriaand silica.

Transferring the polymer-coated particles into an aqueous chemicalmechanical polishing formulation without drying the polymer-coatedparticles reduces agglomeration and irreversible agglomerationexperienced during drying. In addition, agglomeration arising fromdrying the polymer-coated particles has a significant detrimental impactupon yield and can produce coarse particles that adversely impactpolishing. Specifically, maintaining the particles as a dispersionwithout drying facilitates dispersing the polymer-coated particles inaqueous solutions.

In one embodiment, during the manufacture of the abrasive particles, theouter polymeric shell may be crosslinked by employing crosslinkablemonomers in the reactive dispersion. In another embodiment, theinitiator may be added to the reactive dispersion in steps to controlthe thickness of the outer polymeric shell. In yet another embodiment,the non-aqueous solvent may be changed either during or after thereaction. The non-aqueous solvent used during the reaction can beadvantageously selected so as to facilitate compatibilization of theabrasive particles with other fluids that may be used in the polishingcomposition.

The polymer-coated abrasive particles may be subsequently used in apolishing composition for polishing or planarizing substrates, such asmagnetic, optical, semiconductor or silicon substrates. For example, thepolymer-coated particles are particularly effective at polishingpatterned semiconductor wafers. The polymer-coated abrasive particlescomprise an inner particle core and an outer polymeric shell. The innerparticle core has a higher hardness than the outer polymeric shell, andthe polymeric shell advantageously reduces scratching on substratesurfaces. The inner particle core may comprise metals, metalloids,ceramics, intermetallics, organometallics, organoceramics, or acombination comprising at least one of the foregoing. The polymer-coatedparticles are manufactured by reacting a polymeric precursor in thepresence of a particle core. After the reaction, additional liquids andother materials that are used for polishing semiconductor wafers such aswater, corrosion inhibitors, oxidizing agents, chelating or complexingagents, other optional abrasive particles, may be added to the resulteddispersion in order to obtain the polishing composition.

Preferably, the particle core arises directly from a non-aqueousmanufacturing process. This avoids the costs associated with an aqueousto non-aqueous solvent transfer process and facilitates maintaining aspecific particle size distribution. The metals that may be used in theparticle core are transition metals, main group metals, alkaline earthmetals, rare earth metals, or a combination comprising at least one ofthe foregoing metals. Examples of suitable transition metals are iron,nickel, copper, titanium, zinc, molybdenum, or a combination comprisingat least one of the foregoing transition metals. Examples of suitablealkaline earth metals are magnesium, calcium, strontium, barium, or acombination comprising at least one of the foregoing alkaline earthmetals. Examples of suitable main group metals are aluminum, gallium,indium, tin, or a combination comprising at least one of the foregoingmain group metals. Metalloids such as boron, silicon, germanium,tellurium, or a combination comprising at least one of the foregoing maybe use as the particle core.

Ceramics may also be used to form the particle core. Examples ofsuitable ceramic particle cores include the following: inorganic oxides,inorganic hydroxides, inorganic oxides having hydroxide coatings,inorganic carbonates, metal carbides, metal nitrides, metal borides, ora combination comprising at least one of the foregoing particle cores.Particle cores may also comprise metal oxides coated with other metaloxides. Suitable inorganic oxides include, for example, silica (SiO₂),silica particles coated with aluminum hydrous oxide, ellipsoidalparticles of different anisometry coated with silica, silica particlescoated with ceria hydroxide particles, alumina (Al₂O₃), titania (TiO₂),zirconia (ZrO₂), ceria (CeO₂), manganese oxide (MnO₂), vanadium oxide(e.g., V₂O₅, V₂O₃, VO₂), zinc oxide (ZnO), iron oxides (e.g., FeO,α-Fe₂O₃, γ-Fe₂O₃, Fe₃O₄), calcium oxide (CaO), manganese dioxide (MnO₂and Mn₃O₄), alumina coated with silica, titania coated with zirconia, orcombinations comprising at least one of the foregoing inorganic oxides.Examples of suitable inorganic carbides include silicon carbide (SiC),titanium carbide (TiC), tantalum carbide (TaC), tungsten carbide (WC),hafnium carbide (HfC), or a combination comprising at least one of theforegoing carbides. Nitrides such as silicon nitrides (Si₃N₄), titaniumnitride (TiN) may also be used.

Examples of suitable borides are lanthanum boride (LaB₆), praseodymiumboride (PrB₆), neodymium boride (NdB₆), cerium boride (CeB₆), gadoliniumboride (GdB₆), terbium boride (TbB₆), dysprosium boride (DyB₆), holmiumboride (HoB₆), yttrium boride (YB₆), samarium boride (SmB6), europiumboride (EuB₆), erbium boride (ErB₆), thulium boride (TmB₆), ytterbiumboride (YbB₆), lutetium boride (LuB₆), strontium boride (SrB₆), calciumboride (CaB₆), titanium boride (TiB₂), zirconium boride (ZrB₂), hafniumboride (HfB₂), vanadium boride (VB₂), tantalum boride (TaB₂), chromiumborides (CrB and CrB₂), molybdenum borides (MoB₂, Mo₂B₅ and MoB),tungsten boride (W₂B₅), or combinations comprising at least one of theforegoing borides. Diamond can also be advantageously used as theparticle core. Ceramics such as inorganic carbonitrides, silicides,borocarbides, borosilicides, oxycarbonitrides, oxycarbides, may also beused. Preferred particle cores are those that comprise silica oralumina.

The coated particulate may be nanosized or micrometer sized and maycomprise a single particle or multiple particles. When multipleparticles agglomerate or aggregate to form the core, then it is stilldesirable that the cores be nanosized or micrometer sized as detailedbelow. There is no particular limitation to the shape of the particlecores, which may be for example, spherical, irregular, plate-like orwhisker like. Micrometer sized cores may have average dimensions of lessthan or equal to about 2 micrometers (μm). (For purposes of thisspecification, particle size refers to the average particle size and allcompositions represent weight percent, unless specifically notedotherwise.) In one embodiment, the micrometer sized polymer-coatedparticles have average particle sizes of less than or equal to about1.50 μm. In another embodiment, the micrometer sized polymer-coatedparticles have average particle size of less than or equal to about 1.25μm. Although “large” micron sized polymer-coated particles can assistpolishing, sub-micron sized particle may have particular utility. Forexample, coated particles having an average particle size of 5 to 100nanometers (nm) are particularly effective. Most preferably, the coatedparticles have an average particle size of 10 to 75 nm.

The particle cores may generally have average dimensions of less than orequal to about 1000 nanometers (nm). In one embodiment, the cores mayhave average dimensions of less than or equal to about 500 nm. Inanother embodiment, the cores may have average dimensions of less thanor equal to about 100 nm. In yet another embodiment, the cores may haveaverage dimensions of less than or equal to about 75 nm. In yet anotherembodiment, the cores may have average largest dimensions of less thanor equal to about 50 nm. In yet another embodiment, the cores may haveaverage largest dimensions of 5 to 20 nm. As stated above, the nanosizedcores may generally have average dimensions of less than or equal to 200nm. In one embodiment, more than 90% of the cores have averagedimensions less than or equal to 200 nm. In another embodiment, morethan 95% of the particles have average dimensions less than or equal to200 nm. In yet another embodiment, more than 99% of the particles haveaverage dimensions less than or equal to 200 nm with a unimodaldistribution. A unimodal distribution is one that has a single mean forall the particles in the distribution, while a multimodal distributionhas multiple means for all the particles in the distribution. Bimodal orhigher particle size distributions may be used. Preferred cores arespherical in shape and colloidal in size, i.e., the average particlesizes are less than or equal to 100 nm.

The particle cores are present in the reactive dispersion in an amountof 0.1 to about 50 weight percent (wt %), based on the total weight ofthe reactive dispersion. In one embodiment, the particle cores arepresent in an amount of 0.5 to 30 wt %. In another embodiment, theparticle cores are present in the reactive dispersion in an amount of0.75 to about 20 wt %. In yet another embodiment, the particle cores arepresent in an amount of 1 to 10 wt %.

The particle cores possess a layer of polymer coating after the reactionin the reactive dispersion. The polymer coating is in an amount of 0.01to 50 wt %, based on the total weight of the coated particles. In oneembodiment, the polymer coating is present in an amount of 0.1 to 40 wt%. In another embodiment, the polymer coating is present in a amount of0.5 to 30 wt %. In yet another embodiment, the polymer coating ispresent in an amount of 1 to 20 wt %.

The polymer coating on the surface of the particle cores have athickness of 0.1 to 30 nanometers. In one embodiment, the thickness ofthe polymer coating is 0.5 to 20 nanometers. In another embodiment, thethickness of the polymer coating is 1 nanometer to 15 nanometers. In yetanother embodiment, the thickness of the polymer coating is 5 nanometersto 10 nanometers.

The outer polymeric shell covers at least a portion of the outer surfaceof the particle core. Typically, the polymeric shell is softer than theparticle core and therefore facilitates a reduction in the erosion,dishing and scratching during the polishing process. The outer polymericshell may also be varied in thickness to control the removal rate of themetal interconnects or the barrier layer. The thickness and compositionof the outer polymeric shell can be advantageously used to control theselectivity. The outer polymeric shell is generally derived by thereaction of a polymeric precursor in the presence of the core. Thepolymer precursors, as defined herein, comprise reactive species thatare monomeric, oligomeric or polymeric that can undergo additionalpolymerization in the presence of the particle core.

The outer polymeric shell may be derived by the reaction of a monomerwith another monomer or by the reaction of a monomer with a dimer or ahomopolymer comprising a larger number of repeat units such as, forexample, a pentamer, a hexamer, or larger homopolymeric entities. Theouter polymeric shell may also be derived by the reaction of ahomopolymer with another homopolymer if desired. The outer polymericshell may also be crosslinked if desired. The crosslinking may occurduring or after the polymerization. In the preparation of the outerpolymeric shell, a monomer or a reactive species having a larger numberor repeat units are reacted in the presence of the cores and anon-aqueous solvent to form a coating on the cores. The reaction may bebrought about by the presence of a catalyst or an initiator. Thereaction may alternatively be self-catalyzed if desired. The reactioncan occur by addition polymerization, condensation polymerization, freeradical polymerization, or a combination comprising at least one of theforegoing methods of polymerization. Variants of free radicalpolymerization such as emulsion polymerization and ionic polymerizationmay also be conducted to form a coating on the particle cores.

Examples of suitable monomers that may be used to derive the outerpolymeric shell are selected from at least one of silicon containingcompounds (e.g., silanes, cyclic siloxanes); metal containing compounds(e.g., tributyl tin methacrylate, vinyl ferrocene); nitroso containingcompounds (e.g., tri-fluoro-nitrosomethane); aromatic or(cyclo)aliphatic esters (e.g., diallyl pththalates); aromatic compoundssubstituted by hetero atoms/groups (e.g., bisphenol allylether, cinnamicacid, coumarone, vinyl benzene sulfonic acid, chloromethyl styrene,vinyl benzoate); alkenyl aromatic compounds or aromatic compoundssubstituted by hydrocarbyl groups (e.g., divinylbenzene, divinyltoluene,vinyl toluene, styrene, alpha-methyl styrene); (cyclo)aliphatic nitriles(e.g., acrylonitrile, cyanoacrylic acid, cyanoacrylates, vinylidenecyanide); (cyclo)aliphatic aldehydes or ketones (e.g., acrolein,diacetone acrylamide); (cyclo)aliphatic carboxylic acids, anhydrides orsalts (acrylic acid, maleic anhydride, acrylic anhydrides); alcohols(e.g., methanol, ethanol, propanol, dihydric and polyhydric alcohols,ethylene glycol, pentaerythritol, cyclohexane dimethanol);cycloaliphatic alcohols (e.g., allyl alcohol); (cyclo)aliphaticcarboxylic esters (e.g., methyl methacrylate, vinyl acetate, dibutylmaleate, aminoalkyl acrylates); (cyclo)aliphatic halides (e.g.,vinylidene chloride, tetrafluoroethylene, fluoroacrylates);(cyclo)aliphatic hydrocarbons (e.g., ethylene, propylene,tetrafluoroethylene, diisobutylene, norbornene); (cyclo)aliphatichydrocarbons substituted with hydrocarbyl groups (e.g., butadiene,isoprene, allene, dicyclopentadiene, piperylene); triazines (e.g.,melamines, guanamines); isothiocyanates (toluene diisocyanate,isophorone diisocyanate); amides (e.g., ureas); lactams or amino acids(e.g., caprolactam, aminocaproic acid, glutamic acid); amines (aniline,hexamethylene diamine, hexamethylene tetramine, piperidene, ethyleneimine); mono-epoxy compounds (epihalohydrin, ethylene oxide,monoglycidyl ether/ester; glycidol, thiiranes); cyclic ethers (e.g.,tetrahydrofuran); aldehydes; ketones; cyclic thioethers; phenols(monohydric phenols, polyhydric phenols, cresols, resorcinol, bisphenolA); compounds containing carbon-carbon double bonds (trimethylolpropanetriacrylate, diallyl maleate, pentaerythritol tetraacrylate); compoundscontaining carbon-carbon triple bonds (acetylene, propargyl alcohol);compounds containing both carbon-carbon double and carbon-carbon triplebonds (e.g., vinyl acetylene, dimethyl vinyl ethynyl carbinol); andcombinations comprising at least one of the foregoing monomers.

Preferred monomers that may be used to derive the outer polymeric shellare selected from acrolein, acrylic acid, acrylonitrile, adipic acid,bisphenol A, butadiene, caprolactam, chloroprene, diethyl or dimethylterephthalate, ethyl acrylate, ethylene, ethyl methacrylate,formaldehyde, hexamethylene diamine, isobutene, isoprene, maleicanhydride, melamine, methacrylic acid, 2-hydroxyethyl (meth)acrylate,methyl(meth)acrylate, methyl styrene, styrene, divinylbenzene,2,6-naphthalene dicarboxylic acid, phenol, phthalic anhydride,propylene, sebacic acid, styrene, terephthalic acid,tetrafluoroethylene, urea, vinyl acetate, vinyl chloride, vinylidenechloride and a combination comprising at least one of the foregoingmonomers.

Another preferred monomer is an allylic monomer. An allylic monomer isan organic compound comprising at least one, preferably at least two,more preferably at least three allyl (—CH₂—CH═CH₂) groups. Suitableallylic monomers include, for example, diallyl phthalate, diallylisophthalate, triallyl mellitate, triallyl mesate, triallyl benzenes,triallyl cyanurate, triallyl isocyanurate, mixtures thereof, partialpolymerization and products prepared therefrom.

Suitable polyolefins that may be used in the outer polymeric shellinclude linear low density polyethylene (LLDPE), low densitypolyethylene (LDPE), high density polyethylene (HDPE), very low densitypolyethylene (VLDPE), polypropylene (PP), poly ethylene vinyl acetate(PEVA), polyethylene vinyl alcohol (PEVOH), polyethylene propylene diene(PEPD), ethylene propylene rubber (EPR), and combinations comprising atleast one of the foregoing polyolefins. Polyolefins used in themanufacture of the outer polymeric shell may be obtained byZeigler-Natta based polymerization processes or by single site initiated(metallocene catalysts) polymerization processes. As noted above, thesepolymerizations are carried out in the presence of the particle cores.

Blends of other polyolefins such as low density polyethylene, highdensity polyethylene, linear low density polyethylene, polystyrene,polyvinyl chloride, polyamides, polyacrylics, celluloses, polyesters,and polyhalocarbons may also be used in the outer polymeric shell.Copolymers of ethylene with propylene, isobutene, butene, hexene,octene, vinyl acetate, vinyl chloride, vinyl propionate, vinylisobutyrate, allyl alcohol, allyl acetate, allyl acetone, allyl benzene,allyl ether, ethyl acrylate, methyl acrylate, methyl methacrylate,acrylic acid, and methacrylic acid may also be used in the outerpolymeric shell. Various polymers which find wide application inperoxide-cured or vulcanized rubber articles may also be used in theouter polymeric shell, such as, for example, polychloroprene,polybutadiene, polyisoprene, poly(isobutylene), nitrile-butadienerubber, styrene-butadiene rubber, chlorinated polyethylene,chlorosulfonated polyethylene, epichlorohydrin rubber, polyacrylates,butyl or halo-butyl rubbers, or the like, or combinations comprising atleast foregoing polymer resins.

The polyolefins used in the outer shell may or may not be crosslinked.Cross-linking of polyolefins with any additional polymers such as, forexample, those listed above, may be effected through several knownmethods including: (1) use of free radicals provided through the use oforganic peroxides or electron beam irradiation; (2) sulfur cross-linkingin standard EPDM (rubber) curing; (3) and moisture curing ofsilane-grafted materials. Suitable chemical cross-linking agentsinclude, but are not limited to, organic peroxides, preferably alkyl andaralkyl peroxides. Examples of such peroxides include: dicumylperoxide,2,5-dimethyl-2,5-di(t-butylperoxy)hexane,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-di-(t-butylperoxy)-cyclohexane, 2,2′-bis(t-butylperoxy)diisopropylbenzene, 4,4′-bis(t-butylperoxy) butylvalerate,t-butyl-perbenzoate, t-butylperterephthalate, and t-butyl peroxide. Mostpreferably, the cross-linking agent is dicumyl peroxide (Dicup) or2,2′-bis(t-butylperoxy) diisopropylbenzene (Vulcup).

Chemically cross-linked outer polymeric shells can be achieved with theaddition of multi-functional monomeric species, often referred to as“coagents”. Suitable examples of coagents suitable for use in chemicalcross-linking include di- and tri-allyl cyanurates and isocyanurates,alkyl di- and tri-acrylates and methacrylates, zinc-baseddimethacrylates and diacrylates, and 1,2-polybutadiene resins.

A preferred aromatic polyester is a polyarylate. Polyarylates generallyrefers to polyesters of aromatic dicarboxylic acids and bisphenols.Polyarylate copolymers that include carbonate linkages in addition tothe aryl ester linkages, are termed polyester-carbonates, and may alsobe advantageously utilized in the mixtures. The polyarylates can beprepared in solution or by the melt polymerization of aromaticdicarboxylic acids or their ester forming derivatives with bisphenols ortheir derivatives.

The polymer precursor is present in the reactive dispersion an amount of0.01 to 5 wt %, based on the total weight of the reactive dispersion. Inone embodiment, the polymer precursor is present in the reactivedispersion in an amount of 0.1 to 3 wt %, based on the total weight ofthe reactive dispersion. In another embodiment, the polymer precursor ispresent in the reactive dispersion in an amount of 0.2 to 2 wt %, basedon the total weight of the reactive dispersion. In yet anotherembodiment, the polymer precursor is present in the reactive dispersionin an amount of 0.4 to 1 wt %, based on the total weight of the reactivedispersion.

As noted above, the polymer precursor undergoes a reaction to form apolymer. The polymer adsorbs onto the surface of the particle coreduring and after polymerization to form the polymer-coated particle. Thepolymer-coated particles are then used in a polishing composition.

The polymers that may be obtained from the polymerization of the polymerprecursors are thermoplastic polymers, thermosetting polymers, blends ofthermoplastic polymers, blends of thermosetting polymers, or blends ofthermoplastic polymers with thermosetting polymers. The organic polymersmay also be a blend of polymers, copolymers, terpolymers,interpenetrating network polymers or combinations comprising at leastone of the foregoing organic polymers. Examples of thermoplasticpolymers include polyacetals, polyurethanes, polyolefins, polyacrylics,polyester carbonates, polyalkyds, polystyrenes, polyesters, polyamides,polyaramides, polyamideimides, polyarylates, polyarylsulfones,polyethersulfones, polyphenylene sulfides, polysulfones, polyimides,polyetherimides, polytetrafluoroethylenes, polyetherketones, polyetheretherketones, polyether ketone ketones, polybenzoxazoles,polyoxadiazoles, polybenzothiazinophenothiazines, polybenzothiazoles,polypyrazinoquinoxalines, polypyromellitimides, polyquinoxalines,polybenzimidazoles, polyoxindoles, polyoxoisoindolines,polydioxoisoindolines, polytriazines, polypyridazines, polypiperazines,polypyridines, polypiperidines, polytriazoles, polypyrazoles,polycarboranes, polyoxabicyclononanes, polydibenzofurans,polyphthalides, polyacetals, polyanhydrides, polyvinyl ethers, polyvinylthioethers, polyvinyl alcohols, polyvinyl ketones, polyvinyl halides,polyvinyl nitriles, polyvinyl esters, polysulfonates, polysulfides,polythioesters, polysulfones, polysulfonamides, polyureas,polyphosphazenes, polysilazanes, or a combination comprising at leastone of the foregoing organic polymers.

It is generally desirable for the aforementioned polymers to havefunctional groups that may be advantageously used for affectingpolishing performance. For example, functional groups may affectselectivity, removal rate, dishing or planarization of semiconductorsubstrate layers during polishing. The functional groups may also beused for providing compatibility or dispersibility with the non-aqueoussolvent or with the particle cores during the reaction, during themanufacturing of the polishing composition or during the polishingprocess. The functional groups may be covalently bonded to the polymerbackbone or to pendant groups that are covalently bonded to the polymerbackbone. Examples of suitable functional groups are selected from atleast one of bromo groups, chloro groups, iodo groups, fluoro groups,amino groups, peroxide groups, perchlorate groups, perbromate groups,perhalogenated groups, perchlorous groups, hydroxyl groups, thio groups,phosphino groups, alkylthio groups, cyano groups, nitro groups, amidogroups, carboxyl groups, aryl groups, heterocyclyl groups, ferrocenylgroups, heteroaryl groups, alkyl groups, aryl groups, alkaryl groups,aralkyl groups, fluoro substituted alkyl groups, ester groups, ketonegroups, carboxylic acid groups, alcohol groups, fluoro-substitutedcarboxylic acid groups, fluoro-alkyl-triflate groups, and a combinationcomprising at least one of the foregoing functional groups.

The amount of surface coverage provided by the outer polymeric shell,the thickness of the outer polymeric shell and the shell'spolymerization efficiency can be used to control polishing performance,such as, erosion, selectivity, defectivity, planarization efficiency andremoval rate. It can be used to reduce scratching of the surface ifdesired. The outer polymeric shell covers at least a portion of theparticle core. As noted above, the outer polymeric shell may becrosslinked if desired. Optionally, the outer polymeric shell maycomprise polymers that are covalently bonded to the particle core.Preferably, the shell has a physisorbed structure to facilitatemanufacturability of the polymer-coated particles. It is desirable forthe outer polymeric shell to cover the surface of the particle core inan average amount of greater than or equal to 50%, preferably greaterthan or equal to 75%, more preferably greater than or equal to 85%, andmost preferably greater than or equal to 95%. It is desirable for theaverage thickness of outer polymeric shell to be greater than or equalto 0.1 nm, preferably greater than or equal to about 1 nm, and morepreferably greater than or equal to about 5 nm.

The non-aqueous solvent for the reaction is selected for its ability tobe compatible towards the cores as well as the monomers, for its abilityto facilitate the reaction, as well as for its ability to facilitate theadsorption or absorption of the resultant polymers on the cores.Suitable non-aqueous solvent comprises polar liquids, non-polar liquids,ionic liquids, or a combination comprising at least one of the foregoingliquids. Generic examples of suitable polar liquids are alcohols,esters, ketones, ethers, amines, thiols, thioesters, sulfides, anisoles,or a combination comprising at least one of the foregoing polar liquids.Specific examples of suitable polar liquids are water, acetone,propylene carbonate, ethylene carbonate, butyrolactone, dimethylformide, dimethyl sulfoxide, acetonitrile, benzonitrile, methylenechloride, nitromethane, nitrobenzene, sulfolane, dimethylformamide,N-methylpyrrolidone, methanol, acetonitrile, nitromethane, ethanol,propanol, isopropanol, butanol, diethyl ether, tetrahydrofuran, orcombinations comprising at least one of the foregoing polar solvents.Examples of suitable non-polar liquids are hydrocarbons such as benzene,toluene, xylene, hexane, carbon tetrachloride, cyclohexane, heptane,petroleum ether, paraffin wax, or combinations comprising at least oneof the foregoing non-polar solvents. Suitable examples of ionic liquidsare imidazolium, pyridinium derivatives, phosphonium ortetralkylammonium compounds, or a combination comprising at least one ofthe foregoing ionic liquids. Co-solvents that comprise combinations ofpolar liquids, combinations of non-polar liquids and co-solventscomprising at least one polar liquid and at least one non-polar liquidmay also be utilized to modify the solubility of the media.

The non-aqueous solvent may comprise a single liquid or multipleliquids. After the polymerization reaction, preferably removing thesupernatant captures the fine coated particles. Then, the liquid may bereplaced by azeotrope distillation, reverse osmosis or any otherseparation method and replaced with water. Although it is possible toseparate the supernatant directly from the non-aqueous solvent,preferably, removal of the supernatant occurs after transfer to anaqueous-based solution. When divinylbenzene is used as the monomer, analcohol (e.g., isopropanol, butanol) is the preferred non-aqueoussolvent during the reaction. After the reaction, the alcohol isgradually replaced with water. This is called a fluid transfer. Residualalcohol from the fluid transfer process appears to facilitate thesubsequent dispersion of the polymer-coated particles in anaqueous-based polishing composition.

The non-aqueous solvent is present in the reactive dispersion in anamount of 50 to about 99.9 wt %, based on the total weight of thereactive dispersion. In one embodiment, the non-aqueous solvent ispresent in the reactive dispersion in an amount of 70 to about 99 wt %,based on the total weight of the reactive dispersion. In anotherembodiment, the non-aqueous solvent is present in the reactivedispersion in an amount of 80 to about 98 wt %, based on the totalweight of the reactive dispersion. In yet another embodiment, thenon-aqueous solvent is present in the reactive dispersion in an amountof 90 to about 96 wt %, based on the total weight of the reactivedispersion.

As noted above, initiators and catalysts may also be used to polymerizethe reaction of the polymer precursors. Examples of suitable initiatorsand catalysts that may be used to polymerize the reaction of the polymerprecursors are at least one selected from peroxides (e.g.,hydroperoxides); persalts (potassium persulfate); azo compounds (e.g.,azobisisobutyronitrile); free radical and redox catalysts (e.g.,ammonium persulfate, ferrous sulfate, ceric ammonium nitrate); FriedelCrafts catalysts and Lewis acids (e.g., boron tirfluoride (BF₃),aluminum trichloride (AlCl₃), tin chloride (SnCl₄), iron trichloride(FeCl₃), sulfuric acid (H₂SO₄), phosphoric acid (H₃PO₄)); metallocenecatalysts; transition metal catalysts; and a combination comprising atleast one of the foregoing. Typical initiators include free radicals,anionic and cationic initiators consumed in the polymerization process.When divinylbenzene is used as the polymeric precursor, benzoyl peroxideis preferably used as the initiator. The use of an initiator improvesthickness control of the outer polymer shell. For example, increasingthe amount of initiator may increase the thickness of the polymercoating. Furthermore, delaying the introduction of the initiator canalso improve the polymer coating's integrity. Optionally, it is possibleto introduce the initiator in two or more steps to influence thethickness and morphology of the polymer coating.

In one embodiment, in one method of making the polymer coated abrasiveparticles, the particle cores comprising silica or alumina are placed ina non-aqueous solvent comprising a first liquid and a second liquid. Theratio of the first liquid to the second liquid may be adjusted tofacilitate compatibilization of the polymer with the non-aqueoussolvent. This ratio may also be adjusted to facilitate thecompatibilization of the polymer with the particle cores. Whendivinylbenzene is used as the polymer precursor, the first liquid isadvantageously alcohol while the second liquid is advantageously water.The polymer precursor comprising divinylbenzene monomer is added to thenon-aqueous solvent along with the initiator. The reactive dispersionmay be agitated during the reaction. The temperature may also be variedduring the reaction. The divinylbenzene undergoes polymerization to formpolydivinylbenzene and is deposited onto the particle cores to form anouter polymeric shell.

In another embodiment, in another method of making the abrasiveparticles, the particle cores comprising silica or alumina are placed ina non-aqueous solvent comprising only a first liquid. Whendivinylbenzene is used as the polymer precursor, the first liquid isadvantageously alcohol. The polymer precursor comprising divinylbenzenemonomer is added to the non-aqueous solvent along with the initiator.The reactive dispersion may be agitated during the reaction. Thetemperature may also be varied during the reaction. The divinylbenzeneundergoes polymerization to form polydivinylbenzene and is depositedonto the particle cores to form an outer polymeric shell. In oneembodiment, after the formation of the outer polymeric shell, thealcohol may be distilled off and replaced with a second liquid. Apreferred second liquid is deionized water. In another embodiment, afterthe formation of the outer polymeric shell, the reactive mixture may becentrifuged, the supernatant extracted from the centrifuge and subjectedto distillation to replace the alcohol with a second liquid. Thepreferred second liquid is deionized water. It is to be noted that inplace of the centrifuging, other separation processes such as filtrationor reverse osmosis may be used.

During the reaction, the polymer precursor, the particle cores, and theinitiator may be added simultaneously or sequentially. In oneembodiment, in order to control the structure of the polymer formed orthe thickness of the outer polymeric shell the initiator and the polymerprecursor may be added in steps. For example, the polymer precursor maybe added in a first step along with a portion of the initiator. Afterthe reaction has progressed to a certain extent, additional initiator orpolymer precursor may be added in a second step. The rate of addition ofthe initiator may be used to control the thickness of the polymercoating. Similarly, additional polymer or polymer precursor may be addedin a third step. Optionally, if desired, a different polymer precursormay be added to the reactive dispersion during one of the steps to forma copolymer.

In one embodiment, the concentration of the non-aqueous solvent may alsobe changed during the reaction, if desired. Changing the concentrationof the non-aqueous solvent can be undertaken to increase the depositionrate of the polymer onto the surface of the particle cores or to changethe structure of the polymer. For example, in the aforementionedreaction involving divinylbenzene, during the reaction, additionalalcohol may be added to the reactive dispersion. This addition may alsobe carried out in steps if desired. In another embodiment, a third or afourth liquid may be added to the reactive dispersion prior to thereaction, during the course of the reaction, or after the reaction. Theaddition of the third or fourth liquids is undertaken to facilitatecompatibilization, change the rate of reaction, change the structure orthe crosslink density of the outer polymeric shell, change the thicknessof the outer polymeric shell.

One advantageous feature of conducting the reaction in the mannerdescribed above is that there is no need to dry the particles after thedeposition of the outer polymeric shell upon the surface of the particlecores. The drying of the particles prior to manufacturing the polishingcomposition promotes agglomeration of the coated particle cores. This ishighly undesirable as the agglomerated particles have large sizes (i.e.,greater than 1000 nanometers) are generally uneven in size. In yetanother advantageous feature related to this method of forming the outerpolymeric shell, the alcohols that are adsorbed into the shellfacilitate compatibility with water and hence make the particles moredispersible in water. The reactive dispersion, after the reaction, canbe converted to a polishing composition by adding additional water orother desirable liquids, oxidizing agents, compatibilizing agents,chelating agents. A second abrasive comprising uncoated abrasiveparticles may optionally be added to the polishing composition.

Typically, polishing solutions will contain 0.1 to 50 weight percentpolymer-coated abrasive. In addition, the polishing composition mayoptionally include a second abrasive to facilitate “mechanical” removalof cap layers and barrier layers. The abrasive is preferably a colloidalabrasive and may be uncoated if desired. Suitable examples of abrasivesinclude the following: inorganic oxide, inorganic oxides havinghydroxide coatings, metal boride, metal carbide, metal nitride, or acombination comprising at least one of the foregoing abrasives. Suitableinorganic oxides include, for example, silica (SiO₂), silica particlescoated with aluminum hydrous oxide, ellipsoidal particles of differentanisometry coated with silica, silica particles coated with ceriahydroxide particles, alumina (Al₂O₃), titania (TiO₂), zirconia (ZrO₂),ceria (CeO₂), manganese oxide (MnO₂), alumina coated with silica,titania coated with zirconia and combinations comprising at least one ofthe foregoing inorganic oxides. Diamond may also be utilized as anabrasive if desired. Alternative abrasives also include polymericparticles and coated polymeric particles. The preferred abrasive iscolloidal silica.

The polishing composition may also include an oxidizing agent forfacilitating the removal of non-ferrous metal interconnects such asaluminum, aluminum alloys, copper, copper alloys, gold, gold alloys,nickel, nickel alloys, platinum group metals, platinum group alloys,silver, silver alloys, tungsten and tungsten alloys or combinationscomprising at least one of the foregoing metals.

The polishing composition also advantageously comprises a corrosioninhibitor, also commonly termed a film-forming agent. The preferredcorrosion inhibitor is benzotriazole (BTA). Optionally, a supplementarycorrosion inhibitor may be added to the polishing composition.Supplementary corrosion inhibitors are surfactants such as, for example,anionic surfactants, nonionic surfactants, amphoteric surfactants andpolymers, or organic compounds such as azoles.

It is generally preferred to use the polishing composition onsemiconductor substrates having non-ferrous interconnects. Suitablemetals used for the interconnect include, for example, aluminum,aluminum alloys, copper, copper alloys, gold, gold alloys, nickel,nickel alloys, platinum group metals, platinum group alloys, silver,silver alloys, tungsten and tungsten alloys or combinations comprisingat least one of the foregoing metals. The preferred interconnect metalis copper.

The coated particles are advantageous in that they do not agglomerateduring storage or during polishing. The coated particles are alsoadvantageous in that, when the outer polymeric shell is crosslinked, theprocess of polishing does not facilitate a rapid separation or removalof the coating from the particle cores. This feature promotesreproducible results during polishing. The reactive dispersioncontaining the coated particles can be advantageously subjected tochemical processes such as distillation, centrifugation, reverseosmosis, filtration, during the manufacturing of the polishingcomposition, without damaging the coated particles and without promotingany further agglomeration of the particles.

The polymer-coated particles will operate in various fluid media, suchas aqueous-base liquids and non-aqueous liquids. The polishingcomposition enables the polishing apparatus to operate with a lowpressure of less than 21.7 kPa (3 psi). Most preferably, the polishingoccurs with the polishing pad and conditions of the Example shown below.The low polishing pad pressure improves polishing performance byreducing scratching and other undesired polishing defects and reducesdamage to fragile materials such as the low k and ultra-low kdielectrics.

Some embodiments of the invention will now be described in detail in thefollowing Examples.

EXAMPLES Comparative Example A Functionality with poly(2-hydroxyethylmethacrylate)

First, placing 25 g of abrasive particles (silica or alumina as receivedin aqueous slurry) into a 250 ml polypropylene container and addingsec-butanol in 3:1 ratio of alcohol to water formed the initialdispersion. Shaking the dispersion for up to 5 minutes and allowingcoarse particles to settle and decanting a top clear liquid layerwithout disturbing and removing any settled particles provided for aninitial removal of coarse core particles.

This comparative example then followed the following steps: add moresec-butanol and shake again; mark flask for 500 ml volume; add mixtureof particles and alcohol to reaction flask apparatus already set up;wash out bottle with more alcohol and bring total reaction liquid volumeup to 500 ml per 25 grams of particles; heat the reaction mixture whilestirring and allow excess water to be removed via boiling off thewater/alcohol azeotrope (the azeotrope boiling point is 89° C.);continuously add sec-butanol to keep reaction volume constant; when thetemperature reaches 99° C. (all water has been removed), place acondenser in one flask joint and place a stopper in the other flaskjoint; begin refluxing the resulting mixture; when mixture beginsrefluxing, add 2.5 g divinylbenzene monomer to reaction; wait 2 hoursand add 0.25 g benzoyl peroxide initiator for reaction in a 10:1 weightratio of monomer to initiator; continue refluxing; add 1.0 g2-hydroxyethyl methacrylate monomer 2 hours after initiator addition;total reflux time 12 hours; allow reaction to cool and observe whetherany particles settle; if clear supernatant liquid appears due tocoagulation and settling, draw that liquid off for lower volume tocentrifuge; and isolate particles and dry in vacuum oven at 100° C.

The resulting particles were polydivinylbenzene grafted with an outerlayer of poly(2-hydroxyethyl methacrylate) possessing a functionalhydroxyl group. The total amount of polymer coating was approximately 5weight percent. Unfortunately, the resulting particles had anagglomerated structure, were difficult to disperse in aqueouscompositions and provided little or no benefit to chemical mechanicalpolishing.

Comparative Example B Thickness

This test relied upon a similar process to polymer coat particle cores.The recipe was as follows: place 25 g of silica particles (as receivedin aqueous slurry) into a 250 ml polypropylene container; addsec-butanol in 3:1 ratio of alcohol to water; shake solution for up to 5minutes and allow particles to settle; decant top clear liquid layerwithout disturbing and removing any settled particles; add moresec-butanol and shake again. Mark flask for 500 ml volume; add mixtureof particles and alcohol to reaction flask apparatus already set up;wash out bottle with more alcohol and bring total reaction liquid volumeup to 500 ml per 25 grams of particles; heat the reaction mixture whilestirring and allow excess water to be removed via boiling off thewater/alcohol azeotrope (the azeotrope boiling point is 89° C.);continuously add sec-butanol to keep reaction volume constant—when thetemperature reaches 99° C. (all water has been removed); place acondenser in one flask joint and place a stopper in the other flaskjoint; begin refluxing the resulting mixture; and when the mixturebegins refluxing, add divinylbenzene monomer to the reaction; wait 2hours and add appropriate initiator for reaction in a 10:1 weight ratioof monomer to initiator; continue refluxing for a total reflux time of12 hours; allow reaction to cool and see if any particles settle; ifclear supernatant liquid appears due to coagulation and settling, thendraw that liquid off for lower volume to centrifuge; and isolateparticles and dry in vacuum oven at 100° C.

Varying weight ratios of particles to monomer can control the finalcoating thickness. For example, a 10:1 weight ratio of particles tomonomer to achieve a 5 weight percent coating. Unfortunately, theresulting particles had an agglomerated structure, were difficult todisperse in aqueous compositions and provided little or no benefit tochemical mechanical polishing.

Example 1 Polymer-Coated Particles

This test relied upon a liquid-to-liquid transfer process to polymercoat particle cores. The recipe was as follows: place 2678.34 ml IPA ina three-necked 4 L flask; add 471.66 g silica IPA dispersion (25 gsilica by weight from a 31.8% stock dispersion in IPA from Clariant)—twoTeflon paddle blades attached to a glass shaft for mixing; add 50.28 gdivinylbenzene monomer to the reaction mixture and allow the reactionmixture to stir at room temperature for 2 hours; add 5.02 g benzoylperoxide initiator to the reaction mixture while stirring; heat thereaction mixture to reflux; make four additions of 37.55 gdivinylbenzene monomer and 3.75 g benzoyl peroxide initiator after 3,6,9and 12 hours; reflux for 6 hours after the final addition—total refluxtime is 18 hours; cool the reaction mixture and transfer the contents toa Nalgene plastic bottle; ultracentrifuge the reaction mixture at 1,000RPM for 35-40 minutes; decant the resulting supernatant into a 12 Lthree-necked bottle (This supernatant can be further concentrated ifdesired prior to the following solvent transfer by heating underconstant mixing to distill off IPA to the desired amount.); when thesupernatant consists of 30-40% solids, add DI water in sequentialincrements until all IPA has been removed by azeotropic distillation;when the temperature of the distilling solvent reaches 100° C., assumethat all IPA has been removed and water is the only liquid component andallow the resulting aqueous dispersion containing coated silica isallowed to cool and collect into a Nalgene container; agitate thestirred dispersion from above using ultrasonic probe for the period of 5minutes (100 g dispersion per run); then centrifuge the dispersion at1,000 RPM for 15 minutes; and collect the resulting supernatant byvacuum siphoning into a Nalgene bottle.

The resulting particles were unimodal-monodispersible in water,contained 19 wt % polymer and facilitated chemical mechanical polishing.

Example 2 Centrifuge of Polymer-Coated Particles

This example was undertaken to demonstrate the method of coatingparticle cores. In this example, divinylbenzene was polymerized usingbenzoyl peroxide initiator. The polymerization reaction was conducted inisopropanol that contained uncoated silica particle cores. After thereaction, a liquid transfer was undertaken by azeotopic distillation toreplace the isopropanol from the reactive dispersion with water.

An addition of 441.66 milliliters (mL) of isopropanol (IPA) was added toa three-necked 1 liter (L) flask. Then adding 83.34 grams (g) of asilica particle cores (25 g silica particles by weight from a 30% stockdispersion in IPA). The silica dispersion supplied from Clariant andcontained 13 nm particles in the IPA. A Teflon paddle blade attached toa glass shaft maintained the dispersion. While mixing the dispersion,2.5 g of monomer (divinylbenzene) was added to the reaction mixture andthe reaction mixture was stirred at room temperature for a total of 2hours. In addition, 0.25 g of initiator (benzoyl peroxide) was added tothe reaction mixture while stirring. The divinylbenzene reacted to formpolydivinylbenzene (PDVB) and coat the silica particle cores with thePDVB. The reaction mixture was heated and allowed to reflux for 12hours, following that it was cooled and transferred to a 500 ml Nalgenebottle. The reactive dispersion was then centrifuged at 5,000 RPM for 1hour. The resultant supernatant was decanted into a Nalgene plasticbottle and the remaining solids were dried in a vacuum oven at 50° C.

Two different samples were obtained from the aforementioned procedure.The first sample (A) was prepared as follows. The uncentrifuged reactionmixture was distilled until the reactive dispersion contained 30 to 40wt % solids. Deionized water was then added in sequential incrementsuntil all the IPA was removed by distillation. The resulting dispersioncontained 17.0 wt % coated SiO₂ and was collected into a Nalgene plasticcontainer. The resulting dispersion and particles in the dispersion weredried in a vacuum oven at 50° C. and are analyzed below.

The second sample (B) was prepared by taking the supernatant from thecentrifuged reaction material and placing it into a 1 L three-neckedflask. The mixture containing the supernatant was distilled until thereactive dispersion contains 30 to 40 wt % solids. Deionized water wasthen added in sequential increments until all the IPA was removed bydistillation. The resulting dispersion contained 17.0 wt % coated SiO₂and was collected into a Nalgene plastic container. The resultingdispersion and particles in the dispersion dispersion were dried in avacuum oven at 50° C. and are analyzed below.

The resulting particles were analyzed by light scattering using a APVinstrument, manufactured by ALV-Laser Vertriebsgesellschaft m.b.H,Robert-Bosch-Straβe 46, D-63225 Langen, Germany. The samples were firstdiluted to a solids content of about 1 wt %, prior to making themeasurements. Five measurements for each sample were made. The averageof the five readings are shown in the Table 1 below.

TABLE 1 Average Particle Description size (nm) Core Particles 13 PDVBcoated particles in IPA prior to centrifuging 242 Sample A PDVB coatedparticles after phase transferring to 33.5 DI water Sample B PDVB coatedparticles before phase transferring into 18.5 the DI water PDVB coatedparticles after phase transferring into 20 the DI water

From the aforementioned table, it may be seen that the addition of thePDVB coating to the particles increases the average particle size.Further it may be seen that the presence of the surrounding non-aqueoussolvent makes a difference to the average particle size.

Themogravimetric analysis (TGA) conducted on the samples shows thatsample A had a weight loss of 5.7 wt %, indicating that sample A had acoating of about 5.7 wt % PDVB on the particles. Sample B displayed aweight loss of 2.7 wt %, indicating that sample B had a coating of about2.7 wt % PDVB on the particles.

Example 3 Polishing

This example was undertaken to demonstrate the use of silica particlecores coated with polydivinylbenzene. The nomenclature for the materialsused in the polishing compositions for the following examples are shownin Table 2 below. The polishing compositions comprise 1 wt % of silicaparticle cores coated with a polymer. The pH of the polishing solutionwas 3.4.

TABLE 2 Nomenclature Name QRXP-1667 (23K) Rohm and Haas copolymer ofpolyacrylic acid and methacrylic acid having a molecular weight 23,000g/mole. Copolymer 9585 (200K) Rohm and Haas copolymer of polyacrylicacid and methacrylic acid having a molecular weight 200,000 g/mole.Polymer Coated Silica B 3 wt % coating of PDVB on silica Polymer CoatedSilica C 1 wt % coating of PDVB on silica Polymer Coated Silica D 7 wt %coating of PDVB on silica CMC 7L1C1 Carboxymethylcellulose manufacturedby Hercules.

Table 3 shows the various polishing compositions containing coatedparticles that were used in to polish a semiconductor wafer. Polishingexperiments were performed using polishing equipment having model numberIPEC 472. The polishing pad was an IC1000™ (Rohm and Haas ElectronicMaterials CMP Technologies) porous-filled polyurethane polishing pad.The pad was conditioned with a diamond conditioning disk from KinikCompany (model No. AD 3CG-181060) prior to each run. The polishingprocess was performed at a pressure of 1 psi (6.9 kPa), a table speed of80 revolutions per minute (rpm) and a carrier speed of 75 rpm. Thepolishing composition supply rate (slurry flow rate) was 160milliliters/minute (ml/min). All tests employed 200 mm wafers.

TABLE 3 Sample Malic CMC QRXP-1667 Polymer coated Polymer coated Polymercoated # BTA Acid 7L1C1 (23K) (NH₄•2HPO₄) silica B silica C silica DH₂0₂ 1 0.50 0.22 0.32 0.100 0.50 1.000 15 2 0.50 0.22 0.32 0.100 0.501.000 15 3 0.50 0.22 0.32 0.100 0.50 1.000 15

TABLE 4 Sample Copper RR Sheet RR Ratio to Cu # pH (Angstroms/min) TaNTEOS TaN TEOS 1 3.4 2310 200 11 12 214 3007 2 3.4 2611 185 24 14 1102618 3 3.4 3028 129 3 24 953 2887

The above Tables illustrate that the greater the coating of polymer onthe silica particle, the better is the copper to TaN or copper to TEOSselectivity. For example, Sample #3 which has a 7 wt % coating of PDVBon silica shows a copper to TEOS ratio of 953, while Sample #1 which hasa 3 wt % coating of PDVB on silica has a copper to TEOS ratio of 214.Thus by increasing the thickness of the polymer coating on the particlecores, there can be a significant increase in the selectivity displayedby the polishing solution.

1. A method of manufacturing polymer-coated particles useful forchemical mechanical polishing magnetic, optical, semiconductor orsilicon substrates comprising: providing a dispersion of particle coresin a non-aqueous solvent; reacting a polymeric precursor within thedispersion to polymerize the polymeric precursor to form a polymer andto coat the particle cores with the polymer, the polymeric precursorbeing monomeric or oligomeric and the polymer coating at least a portionof the surface of the particle cores with the polymer and forming thepolymer-coated particles having a solid outer polymeric shell;substituting the non-aqueous solvent with water to form an aqueousmixture containing the polymer-coated particles; and forming an aqueouschemical mechanical polishing formulation with the polymer-coatedparticles without drying the polymer-coated particles.
 2. The method ofclaim 1 including the additional step of separating the polymer-coatedparticles as a supernatant.
 3. The method of claim 1 wherein the aqueoussubstituting step relies upon azeotropic distilling to remove thenon-aqueous solvent from the polymer-coated particles.
 4. The method ofclaim 1 including the additional step of attaching functional groups tothe polymer-coated particles.
 5. The method of claim 1 wherein thedispersing particles in the non-aqueous solvent occurs without anearlier solvent transfer from an aqueous solution.
 6. A method ofmanufacturing polymer-coated particles useful for chemical mechanicalpolishing magnetic, optical, semiconductor or silicon substratescomprising: providing a dispersion of particle cores in a non-aqueoussolvent; reacting a polymeric precursor within the dispersion topolymerize the polymeric precursor to form a polymer and to coat theparticle cores with the polymer, the polymeric precursor being monomericor oligomeric and the polymer coating at least a portion of the surfaceof the particle cores with the polymer and forming the polymer-coatedparticles having a solid outer polymeric shell; substituting thenon-aqueous solvent with water to form an aqueous mixture containing thepolymer-coated particles; and forming an aqueous chemical mechanicalpolishing formulation with an aqueous dispersion of the polymer-coatedparticles without drying the polymer-coated particles.
 7. The method ofclaim 6 including the additional step of separating the polymer-coatedparticles as a supernatant.
 8. The method of claim 6 wherein the aqueoussubstituting step relies upon azeotropic distilling to remove thenon-aqueous solvent from the polymer-coated particles.
 9. The method ofclaim 6 including the additional step of attaching functional groups tothe polymer-coated particles.
 10. The method of claim 6 wherein thedispersing particles in the non-aqueous solvent occurs without anearlier solvent transfer from an aqueous solution.